WO2011102523A1 - 水系熱処理液組成物 - Google Patents
水系熱処理液組成物 Download PDFInfo
- Publication number
- WO2011102523A1 WO2011102523A1 PCT/JP2011/053778 JP2011053778W WO2011102523A1 WO 2011102523 A1 WO2011102523 A1 WO 2011102523A1 JP 2011053778 W JP2011053778 W JP 2011053778W WO 2011102523 A1 WO2011102523 A1 WO 2011102523A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heat treatment
- treatment liquid
- liquid composition
- performance
- cooling
- Prior art date
Links
- 0 CCOCC(CO)OCC(C*C)OCC(CN)OCC(C*1*C(CO)C1)OCC(COC(COC(CO)COC(CO)COC)OC(COC(C*)CO)COC(C*C)CO)*CC(COCC(CC(C)*)N=O)*C(*)CONC Chemical compound CCOCC(CO)OCC(C*C)OCC(CN)OCC(C*1*C(CO)C1)OCC(COC(COC(CO)COC(CO)COC)OC(COC(C*)CO)COC(C*C)CO)*CC(COCC(CC(C)*)N=O)*C(*)CONC 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/60—Aqueous agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/081—Inorganic acids or salts thereof containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/242—Hot working
Definitions
- the present invention relates to an aqueous heat treatment liquid composition used for quenching metal parts.
- Heat treatment liquids used for quenching metal parts are roughly classified into oil systems and water systems (aqueous solutions), and oil systems are widely used. This is because the oil-based heat treatment liquid has an appropriate cooling performance, has a small quenching distortion, and does not have the risk of occurrence of quenching cracks.
- the water-based heat treatment liquid is used because the oil-based heat treatment liquid has a low cooling rate and insufficient cooling performance.
- the water-based heat treatment liquid has a higher cooling performance than the oil-based heat treatment liquid, uneven cooling tends to occur and there is a risk of burning cracks.
- a composition in which a water-soluble polymer is added to an aqueous heat treatment liquid is known to prevent burning cracks.
- the water-soluble polymer adheres to the surface of the metal part, inhibits heat transfer, and suppresses cooling performance.
- the aqueous heat treatment liquid composition to which a water-soluble polymer is added is widely used industrially, and polyalkylene glycol (PAG) is the mainstream as the water-soluble polymer.
- PAG polyalkylene glycol
- such a water-based heat treatment liquid composition has a drawback that the vapor film stage is long, and therefore cooling unevenness easily occurs.
- an aqueous heat treatment liquid composition has been proposed in which a low-molecular-weight glycol is added to a high-molecular-weight polyalkylene glycol, thereby shortening the vapor film stage and improving the cooling unevenness performance (see Patent Document 1). .
- quenching with a saline solution has been known for a long time as a technique for improving the uneven cooling performance. Since the salt solution does not have a vapor film stage, it has a high cooling performance and a high cooling nonuniformity performance, and has few burning cracks (see Non-Patent Document 1).
- Patent Document 1 Even the aqueous heat treatment liquid composition of Patent Document 1 does not always have sufficient cooling resistance. Further, the saline solution of Non-Patent Document 1 hardly rusts industrially because rust is generated in an extremely short time within 1 hour after the heat treatment, and corrosion to equipment such as an oil tank is remarkable.
- an object of the present invention is to provide an aqueous heat treatment liquid composition having a high cooling performance and an uneven cooling resistance while having a good antirust performance.
- the present invention provides the following aqueous heat treatment liquid composition.
- An aqueous heat treatment liquid composition comprising hyperbranched polyglycerol.
- the hyperbranched polyglycerol has a mass average absolute molecular weight of 5,000 or more and 100,000 or less.
- the amount of the hyperbranched polyglycerol is 3% by mass or more and 30% by mass based on the total amount of the composition %
- a water-based heat treatment liquid composition characterized by the above.
- aqueous heat treatment liquid composition of the present invention is formulated with hyperbranched polyglycerol, it exhibits excellent rust prevention performance while having high cooling performance and uneven cooling performance.
- composition aqueous heat treatment liquid composition of the present invention
- HBP-PGR hyperbranched polyglycerol
- HBP-PGR blended in the composition of the present invention is a hyperbranched polymer represented by the following chemical formula (1) obtained by ring-opening polymerization of glycidol, for example.
- HBP-PGR has a branched structure in the repeating unit of glycidol.
- the composition containing the HBP-PGR of the present invention has high cooling performance and uneven cooling performance, and also has good antirust performance.
- the aqueous polymer solution is stirred to suppress the occurrence of uneven cooling.
- the stirring efficiency is partially reduced depending on the size and shape of the metal part. In the portion where the stirring efficiency is low, the cooling rate is relatively slow, so that uneven cooling is likely to occur.
- the ease of occurrence of uneven cooling can be evaluated by the difference in cooling time depending on the presence or absence of stirring.
- the conventional polymer aqueous solution for example, as shown in FIG.
- the difference in cooling time is large, so that uneven cooling tends to occur.
- the composition of the present invention for example, as shown in FIG. 2, there is almost no vapor film stage, and there is almost no difference in cooling time depending on the presence or absence of stirring, so the cooling rate is fast and the occurrence of cooling unevenness. (Specific experimental conditions will be described later).
- the composition of the present invention exhibits high uneven cooling performance.
- a polymer film is not formed on the surface of a metal part, so that higher cooling performance and cooling resistance unevenness performance can be exhibited.
- the blending amount of HBP-PGR is preferably 3% by mass or more and 30% by mass or less based on the total amount of the composition. If the blending amount of HBP-PGR is 3% by mass or more, the uneven cooling performance can be sufficiently exhibited. On the other hand, when the blending amount of HBP-PGR is 30% by mass or less, the increase in viscosity is suppressed and the metal part does not require a sticky cleaning process. Therefore, a preferable range of the blending amount of HBP-PGR is 5% by mass or more and 15% by mass or less.
- the mass average absolute molecular weight of HBP-PGR is preferably 5,000 or more and 500,000 or less. If the mass average absolute molecular weight of HBP-PGR is 5,000 or more, good viscosity can be obtained, and cooling performance and uneven cooling performance can be sufficiently exhibited. On the other hand, if the mass average absolute molecular weight of HBP-PGR is 500,000 or less, the polymer chain is hardly cleaved, the generation of low molecules can be suppressed, and cooling performance and uneven cooling performance can be sufficiently exhibited. Therefore, a preferable range of the mass average absolute molecular weight is 5,000 or more and 100,000 or less.
- the mass average absolute molecular weight of HBP-PGR can be measured by size exclusion chromatography online-multi-angle light scattering (SEC-MALLS) method using a 0.2 mol / L NaNO 3 aqueous solution as a mobile phase solvent.
- SEC-MALLS size exclusion chromatography online-multi-angle light scattering
- the branching degree of HBP-PGR is 0.40 or more and 0.65 or less, preferably 0.45 or more and 0.55 or less.
- the degree of branching of HBP-PGR can be measured by the following method.
- Measurement conditions 200 mg of polymer dissolved in 0.6 mL of heavy water Device used: 100 MHz 13 C-NMR [manufactured by JEOL Ltd., “JEOLJNM-A400II”] Measurement conditions: 13 C-NMR measurement with inverted gate (nne 13 C-NMR), pulse interval time 7 seconds Acetone is used as a standard peak ( ⁇ : 30.89 ppm).
- Method for producing HBP-PGR As a method for producing HBP-PGR, glycidol as a monomer is subjected to ring-opening polymerization using a BF 3 complex as an initiator.
- the BF 3 complex used as the initiator include BF 3 ⁇ ethyl ether complex [(C 2 H 5 ) 2 O ⁇ BF 3 ], BF 3 ⁇ phenol complex [(C 6 H 5 OH) 2 ⁇ BF.
- BF 3 ⁇ monoethylamine complex [C 2 H 5 NH 2 ⁇ BF 3 ]
- BF 3 ⁇ n-butyl ether complex [(n-C 4 H 9 ) 2 O ⁇ BF 3 ] and the like.
- BF 3 ⁇ ethyl ether complex is preferable from the viewpoint of performance as an initiator.
- an organic solvent which is inert to the reaction and can sufficiently dissolve the initiator, the monomer glycidol and the product HBP-PGR can be used. Is preferred.
- a reactor equipped with a stirring device and a glycidol charging device is charged with methylene chloride as a solvent and BF 3 ⁇ ethyl ether complex as an initiator, While stirring the solution containing the agent, glycidol is gradually added thereto.
- the input amount of the BF 3 ⁇ ethyl ether complex is 1 mmol or more and 10 mmol or less, preferably 2 mmol or more and 6 mmol or less per liter of the solvent.
- the charging rate of glycidol is 0.05 mol / h or more and 1.0 mol / h or less, preferably 0.1 mol / h or more and 0.5 mol / h or less per liter of the solvent.
- the polymerization temperature is preferably ⁇ 30 ° C. or higher and 10 ° C. or lower, more preferably ⁇ 20 ° C. or higher and 0 ° C. or lower.
- the total amount of glycidol added is 300 mol or more and 1,800 mol or less, preferably 400 mol or more and 1,600 mol or less with respect to 1 mol of BF 3 ⁇ ethyl ether complex. It is.
- the optimum conditions are selected according to the size of the reaction apparatus and the shape of the stirring apparatus. After charging glycidol, further stirring is performed at the polymerization temperature to continue the polymerization.
- the total polymerization time depends on the polymerization temperature, the amount of initiator and glycidol charged, and cannot be determined in general, but is usually 20 hours or more and 50 hours or less. In this way, by performing ring-opening polymerization and appropriately selecting each of the above conditions, the mass average absolute molecular weight of HBP-PGR can be controlled, and HBP-PGR can be obtained with good reproducibility.
- the composition of the present invention preferably further contains a water-soluble rust inhibitor.
- the blending amount of the water-soluble rust preventive is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.03 on the basis of the total amount of the composition from the viewpoint of improvement in rust prevention performance and economic balance. It is at least 1% by mass.
- water-soluble rust preventives include aliphatic monocarboxylates such as octanoate and nonanoate, aliphatic branched carboxylates such as isononanoate and neodecanoate, octanedioic acid (suberic acid) salt, Examples thereof include aliphatic dicarboxylic acid salts such as decanedioic acid (sebacic acid) salt and dodecanedioic acid. For example, potassium sebacate, ethanolamine salt of dodecanedioic acid and the like are preferably used.
- aromatic carboxylate may be sufficient.
- piperazine derivatives such as monohydroxymonoethylpiperazine can be suitably used as the water-soluble rust preventive.
- the composition of the present invention may further contain additives commonly used in the heat treatment liquid, such as an antioxidant and a cleaning dispersant.
- the composition of the present invention can exhibit excellent cooling performance, uneven cooling performance and rust prevention performance in the heat treatment of metal parts, and therefore various kinds of materials such as carbon steel, nickel-manganese steel, chromium-molybdenum steel, manganese steel, etc. It can be suitably used as a heat treatment liquid for alloy steel. Moreover, in order to heat-treat metal parts, such as steel materials, using the composition of this invention, the temperature of the composition which is heat processing liquid is set to the temperature (about 40 degreeC) of normal heat processing. When the cooling performance is controlled, the temperature of the composition may be as high as possible at 100 ° C. or lower.
- composition of the present invention exhibits rust prevention performance while having high cooling performance and uneven cooling performance
- heat treatment used for immersion quenching, induction quenching, cooling during solution treatment of aluminum or the like It can be suitably used as a liquid.
- the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
- the cooling performance, cooling unevenness performance, and rust prevention performance of the aqueous heat treatment liquid composition were evaluated by the following methods.
- Example 1 and 2 and Comparative Examples 1 to 5 A predetermined amount of the following compounding agent was blended in water to prepare an aqueous heat treatment liquid composition, which was used as a sample liquid.
- the composition is shown in Table 1.
- Mw mass average absolute molecular weight
- SEC-MALLS size exclusion chromatography online-multi-angle light scattering
- Detector 1 Multi-angle light scattering detector (manufactured by Wyatt, “DAWN 8”)
- Detector 2 Viscosity detector (Wyatt, “Viscostar”)
- Detector 3 Refractive index (RI) detector (manufactured by Wyatt, “Optilab rEX”)
- Measurement of average molecular weight distribution mass average absolute molecular weight (Mw) / number average molecular weight (Mn), Mw and Mn are standard polystyrene conversion values) It was obtained by the SEC-MALLS method using the apparatus and conditions described in (2) above.
- (4) Measurement of degree of branching (DB) The degree of branching (DB) was determined according to the method described in the specification text.
- ⁇ Cooling resistance performance Based on the time (seconds) during which the casting is cooled from 800 ° C. to 150 ° C. without stirring the sample solution at a liquid temperature of 40 ° C., the sample solution at a liquid temperature of 40 ° C. is stirred at a flow rate of 10 cm / sec. The cooling unevenness performance was evaluated by the difference in the cooling time from the cooling time to 150 ° C.
- Rust prevention performance is indicated by the following five-stage numerical value. 0: No rust 1: Trace of rust (no more than 3 spot-like rust) 2: Slight rust (4 or more spot-like rusts are generated) 3: Medium rust (a spot-like rust is generated on the entire casting) 4: Severe rust (rust occurs on the entire casting surface)
- the cooling unevenness performance is comparable to that in the case.
- the difference in cooling time is 0.7 to 3.0 seconds, which indicates that uneven cooling is likely to occur.
- the sample solution of Example 1 has a rust prevention performance that does not cause a problem in practice, and the sample solution of Example 2 to which a water-soluble rust inhibitor is added further improves the rust prevention performance. . That is, it can be seen that the rust prevention performance can be set freely.
- the antirust performance of the sample liquid of Example 1, 2 is comparable as the sample liquid from the comparative example 1 which mixed PAG etc. to the comparative example 3.
- the salt solution of the comparative example 5 which added the water-soluble rust preventive agent hardly changes rust prevention performance with the salt solution of the comparative example 4 which does not add the water-soluble rust preventive agent.
- the present invention can be used as a water-soluble cooling liquid for heat treatment having excellent cooling performance and uneven cooling performance and excellent rust prevention performance.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Lubricants (AREA)
Abstract
Description
一方、特に大きな金属部品や、焼入れ性の悪い金属部品の場合、油系熱処理液では、冷却速度が遅く、冷却性能が不足するので、水系熱処理液が用いられる。ところが、水系熱処理液は、油系熱処理液よりも冷却性能が高いので、冷却むらが生じやすく焼割れのおそれがある。
そこで、高分子量のポリアルキレングリコールに低分子量のグリコールを添加することで、蒸気膜段階を短くし、耐冷却むら性能を向上させた水系熱処理液組成物が提案されている(特許文献1参照)。
一方、耐冷却むら性能を高くする技術として、古くから食塩水による焼入れが知られている。食塩水は、蒸気膜段階が無いので、高い冷却性能を有しながら耐冷却むら性能が高く焼割れが少ない(非特許文献1参照)。
また、非特許文献1の食塩水では、熱処理後1時間以内という極めて短時間で錆が発生し、油槽等の設備への腐食も著しいことから工業的にはほとんど使用できない。
[1]ハイパーブランチ型ポリグリセロールを配合してなることを特徴とする水系熱処理液組成物。
[2]上記[1]に記載の水系熱処理液組成物において、前記ハイパーブランチ型ポリグリセロールの質量平均絶対分子量が5,000以上、500,000以下であることを特徴とする水系熱処理液組成物。
[3]上記[2]に記載の水系熱処理液組成物において、前記ハイパーブランチ型ポリグリセロールの質量平均絶対分子量が5,000以上、100,000以下であることを特徴とする水系熱処理液組成物。
[4]上記[1]から上記[3]までのいずれか1つに記載の水系熱処理液組成物において、前記ハイパーブランチ型ポリグリセロールの配合量が組成物全量基準で3質量%以上、30質量%以下であることを特徴とする水系熱処理液組成物。
[5]上記[1]から上記[4]までのいずれか1つに記載の水系熱処理液組成物において、さらに水溶性防錆剤が配合されていることを特徴とする水系熱処理液組成物。
[6]上記[1]から上記[5]までのいずれか1つに記載の水系熱処理液組成物において、浸漬焼入れ、高周波焼入れ、及び、溶体化処理時の冷却のいずれかに用いられることを特徴とする水系熱処理液組成物。
従来のポリマー水溶液を用いて焼入れした場合では、蒸気膜段階が長いので、冷却むらが発生しやすい。それ故、ポリマー水溶液を攪拌して冷却むらの発生を抑制している。しかし、金属部品の大きさや形状によって部分的に撹拌効率が低くなる。攪拌効率の低い部分では、相対的に冷却速度が遅くなるので冷却むらが発生しやすい。ここで、冷却むらの発生の起こり易さは、攪拌の有無による冷却時間の差によって評価できる。従来のポリマー水溶液では、例えば、図1に示すように、冷却時間の差が大きいので冷却むらが起こりやすい。
これに対して、本発明の組成物では、例えば、図2に示すように、蒸気膜段階がほとんどなく、攪拌の有無による冷却時間の差もほとんどないので、冷却速度が速く、冷却むらの発生を抑制できる(具体的な実験条件については後述する)。特に、金属部品が大きい場合や形状が複雑な場合でも本発明の組成物は高い耐冷却むら性能を発揮する。
また、本発明の組成物では、従来のポリマー水溶液と異なり、金属部品の表面にポリマー膜を形成することがないので、さらに高い冷却性能及び耐冷却むら性能を発揮できる。
HBP-PGRの配合量が3質量%以上であれば、耐冷却むら性能を十分に発揮することができる。一方、HBP-PGRの配合量が30質量%以下であれば、粘性が高くなるのを抑え、金属部品がべたつき洗浄工程を必要とすることもない。
それ故、好ましいHBP-PGRの配合量の範囲は、5質量%以上、15質量%以下である。
HBP-PGRの質量平均絶対分子量が5,000以上であれば良好な粘性を得ることができ、冷却性能や耐冷却むら性能を十分に発揮することができる。一方、HBP-PGRの質量平均絶対分子量が500,000以下であれば、ポリマー鎖が切断されにくく、低分子の生成を抑制し、冷却性能や耐冷却むら性能を十分に発揮することができる。
それ故、好ましい質量平均絶対分子量の範囲は、5,000以上、100,000以下である。
測定条件:ポリマー200mgを重水0.6mLに溶解
使用装置:100MHz13C-NMR[日本電子株式会社製、「JEOLJNM-A400II」]
測定条件:反転ゲート付13C-NMR測定(nne13C-NMR)、パルス間隔時間7秒 アセトンを標準ピーク(δ:30.89ppm)として測定を行う。
積算回数:4000回
積分に用いている各ピーク範囲
・L1:60.75-62.12ppm
・T :62.68-63.35ppm
・L2:72.01-73.38ppm(このピークの積分値には炭素2つ分含まれているので、計算時はその半分の値とする)
・D :76.93-79.68ppm
上記各ピーク範囲については、図3の13C-NMRスペクトルで示す。
分岐度(DB)は、上記各ピークの積分値から、下記式(2)によって算出される。
分岐度(DB)=2D/(2D+L1+L2/2) ・・・(2)
HBP-PGRの製造方法としては、モノマーであるグリシドールを、開始剤としてBF3錯体を用い、開環重合させる。この際、開始剤として用いるBF3錯体としては、例えばBF3・エチルエーテル錯体[(C2H5)2O・BF3]、BF3・フェノール錯体[(C6H5OH)2・BF3]、BF3・モノエチルアミン錯体[C2H5NH2・BF3]、BF3・n-ブチルエーテル錯体[(n-C4H9)2O・BF3]などが挙げられる。これらの中で、開始剤としての性能の上から、BF3・エチルエーテル錯体が好ましい。
この開環重合における溶媒としては、反応に不活性であって、開始剤、モノマーのグリシドール及び生成物のHBP-PGRを、充分に溶解し得る有機溶媒を用いることができるが、特にメチレンクロライドが好適である。
また、グリシドールの投入速度は、溶媒1L当たり、0.05モル/h以上、1.0モル/h以下、好ましくは0.1モル/h以上、0.5モル/h以下である。重合温度は、好ましくは-30℃以上、10℃以下、より好ましくは-20℃以上、0℃以下である。
グリシドールの全投入量は、HBP-PGRの収率の面から、BF3・エチルエーテル錯体1モルに対して、300モル以上、1,800モル以下、好ましくは400モル以上、1,600モル以下である。
このようにして、開環重合を行い、上記各条件を適宜選定することにより、HBP-PGRの質量平均絶対分子量の制御が可能となると共に、HBP-PGRを再現性よく得ることができる。
なお、この開環重合反応においては、反応系においてモノマーが少ない条件下では、分子内環化(バックバイティング)が生じやすい。したがって、グリシドールの投入速度が遅すぎる場合や、重合時間が長すぎる場合には、分子内環化が生じやすく、低分子量化や収率の低下をもたらすことがある。
反応終了後、例えば下記の操作を行うことにより、開環重合で生成したHBP-PGRを、効率よく取得することができる。
即ち、アンモニア水等により反応停止後、溶媒を留去し、残渣をメタノールに溶解し、アセトンで再沈殿することにより、HBP-PGRを高純度で得ることができる。
また、水溶性防錆剤としては、モノヒドロキシモノエチルピペラジン等のピペラジン誘導体等も好適に用いることができる。
本発明の組成物には、さらに、熱処理液に汎用される添加剤、例えば酸化防止剤、および清浄分散剤などが配合されていてもよい。
また、本発明の組成物を用いて、鋼材等の金属部品を熱処理するには、熱処理液である組成物の温度を、通常の熱処理の温度(40℃程度)に設定する。なお、冷却性能を制御した場合は、組成物の温度を100℃以下で出来るだけ高くしても良い。
以下に示す配合剤を水に所定量配合して水系熱処理液組成物を調製し、試料液とした。配合組成を表1に示す。
(1.1)熱処理剤
ハイパーブランチ型ポリグリセロール(HBP-PGR):質量平均絶対分子量(Mw)=10,000、分子量分散度(Mw/Mn)=3.08、分岐度(BD)=0.51
ポリアルキレングリコール(PAG):質量平均絶対分子量(Mw)=40,000
エチレングリコールモノブチルエーテル及びプロピレングリコール:市販品
(1.2)水溶性防錆剤
セバシン酸カリウム及びモノヒドロキシモノエチルピペラジン:市販品
(1.3)食塩:市販品
HBP-PGR及びPAGの質量平均絶対分子量は、下記の装置及び条件により、サイズ排除クロマトグラフィーオンライン-多角度光散乱(SEC-MALLS)法により測定した。なお、標準サンプルとしてポリスチレンを用いた。
分離カラム:Tosoh TSKgel GMPWXLcolumns(linear,7.5mm×600mm;exclusion limit,5×107)を2本使用
カラム温度:40℃
移動相溶媒:0.2mol/L濃度NaNO3水溶液
移動相流速:1.0mL/min
試料濃度 :3g/mL
注入量 :100μL
検出器1:多角度光散乱検出器(Wyatt社製、「DAWN 8」)
検出器2:粘度検出器(Wyatt社製,「Viscostar」)
検出器3:屈折率(RI)検出機(Wyatt社製,「Optilab rEX」)
(3)平均分子量分布の測定(質量平均絶対分子量(Mw)/数平均分子量(Mn)、Mw及びMnは標準ポリスチレン換算値)
上記(2)の装置及び条件を用い、SEC-MALLS法により得た。
(4)分岐度(DB)の測定
明細書本文に記載の方法に従って求めた。
以下に示す方法で、上記各試料液について冷却性能、耐冷却むら性能、防錆性能を評価した。
JIS K 2242の冷却性能測定方法に準拠して評価した。すなわち、液温40℃の試料液を攪拌しない状態で鋳物が800℃から150℃まで冷却される時間(秒)を測定し、その冷却時間により冷却性能を評価した。
液温40℃の試料液を攪拌しない状態で鋳物が800℃から150℃まで冷却される時間(秒)を基準とし、液温40℃の試料液を流速10cm/秒で攪拌した状態で800℃から150℃まで冷却される時間との冷却時間の差により耐冷却むら性能を評価した。
DIN 51360-12-Aに準拠して評価した。すなわち、鋳物切粉をシャーレ内のろ紙上に2gとり、試料液を2ml滴下し、2時間放置後の状態を評価した。防錆性能は以下に示す5段階の数値で示される。
0:錆無し
1:錆の痕跡(点状の錆が3つ以下発生)
2:僅かな錆(点状の錆が4つ以上発生)
3:中度の錆(鋳物の全体的に点状の錆が発生)
4:重度の錆(鋳物の全面に錆が発生)
表1及び図2,4,5に示すように、HBP-PGRを配合した実施例1,2の試料液では、冷却時間が1.0秒であり、比較例4,5の試料液(食塩水)を用いた場合と同程度の冷却性能であることがわかる。一方、PAGを配合した比較例1から比較例3までの試料液では、冷却時間が7.8~10.5秒であり、冷却速度が遅く冷却性能が低いことがわかる。
また、表1及び図2,5に示すように、実施例1,2の試料液の冷却時間の差が0.02又は0.03秒であり、比較例4,5の食塩水を用いた場合と同程度の耐冷却むら性能であることがわかる。一方、PAG等を配合した比較例1から比較例3までの試料液では、冷却時間の差が0.7~3.0秒であり、冷却むらが発生しやすいことがわかる。
そして、実施例1の試料液では実用上問題にならない程度の防錆性能を有し、また、水溶性防錆剤を添加した実施例2の試料液では防錆性能がさらに向上することがわかる。すなわち、防錆性能を自由に設定できることがわかる。また、実施例1,2の試料液の防錆性能は、PAG等を配合した比較例1から比較例3までの試料液と同程度であることがわかる。一方、水溶性防錆剤を添加した比較例5の食塩水は、水溶性防錆剤を添加していない比較例4の食塩水とほとんど防錆性能は変わらないことがわかる。
Claims (6)
- ハイパーブランチ型ポリグリセロールを配合してなる
ことを特徴とする水系熱処理液組成物。 - 請求項1に記載の水系熱処理液組成物において、
前記ハイパーブランチ型ポリグリセロールの質量平均絶対分子量が5,000以上、500,000以下である
ことを特徴とする水系熱処理液組成物。 - 請求項2に記載の水系熱処理液組成物において、
前記ハイパーブランチ型ポリグリセロールの質量平均絶対分子量が5,000以上、100,000以下である
ことを特徴とする水系熱処理液組成物。 - 請求項1から請求項3までのいずれか1項に記載の水系熱処理液組成物において、
前記ハイパーブランチ型ポリグリセロールの配合量が組成物全量基準で3質量%以上、30質量%以下である
ことを特徴とする水系熱処理液組成物。 - 請求項1から請求項4までのいずれか1項に記載の水系熱処理液組成物において、
さらに水溶性防錆剤が配合されている
ことを特徴とする水系熱処理液組成物。 - 請求項1から請求項5までのいずれか1項に記載の水系熱処理液組成物において、
浸漬焼入れ、高周波焼入れ、及び、溶体化処理時の冷却のいずれかに用いられる
ことを特徴とする水系熱処理液組成物。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/580,305 US9023234B2 (en) | 2010-02-22 | 2011-02-22 | Aqueous heat treatment liquid composition |
CN201180010380.1A CN102753709B (zh) | 2010-02-22 | 2011-02-22 | 水系热处理液组合物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-035690 | 2010-02-22 | ||
JP2010035690A JP5475497B2 (ja) | 2010-02-22 | 2010-02-22 | 水系熱処理液組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011102523A1 true WO2011102523A1 (ja) | 2011-08-25 |
Family
ID=44483106
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/053778 WO2011102523A1 (ja) | 2010-02-22 | 2011-02-22 | 水系熱処理液組成物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US9023234B2 (ja) |
JP (1) | JP5475497B2 (ja) |
CN (1) | CN102753709B (ja) |
WO (1) | WO2011102523A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6235997B2 (ja) * | 2012-03-02 | 2017-11-22 | 出光興産株式会社 | 水系冷却剤 |
JP6227248B2 (ja) * | 2012-12-27 | 2017-11-08 | 出光興産株式会社 | 水系冷却剤 |
CN108884505B (zh) * | 2016-03-31 | 2021-03-19 | 出光兴产株式会社 | 水溶性淬火油组合物 |
CN108884504B (zh) | 2016-03-31 | 2021-01-26 | 出光兴产株式会社 | 水溶性淬火油组合物 |
WO2019083973A1 (en) * | 2017-10-23 | 2019-05-02 | Novelis Inc. | REACTIVE DEACTIVATION SOLUTIONS AND METHODS OF USE |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50109106A (ja) * | 1974-02-01 | 1975-08-28 | ||
JPS60501316A (ja) * | 1983-05-18 | 1985-08-15 | イ−・エフ・ホ−トン・アンド・カンパニ− | 置換オキサゾリン重合体を使用した急冷方法 |
JPH01100217A (ja) * | 1987-10-14 | 1989-04-18 | Idemitsu Kosan Co Ltd | 焼入剤 |
JPH09227932A (ja) * | 1996-02-21 | 1997-09-02 | Idemitsu Kosan Co Ltd | 水溶性焼入れ液 |
JP2002265973A (ja) * | 2001-03-07 | 2002-09-18 | Daido Chem Ind Co Ltd | 水溶性熱処理液 |
JP2009185179A (ja) * | 2008-02-06 | 2009-08-20 | Nagasaki Univ | 多分岐性高分子及びその製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4486246A (en) | 1983-05-18 | 1984-12-04 | E. F. Houghton & Co. | Polyoxazolines in aqueous quenchants |
US4528044A (en) | 1983-12-16 | 1985-07-09 | E. F. Houghton & Co. | Aqueous quenchants containing polyoxazolines and n-vinyl heterocyclic polymers and their use in quenching steel |
SE9602464L (sv) * | 1996-06-24 | 1997-05-20 | Perstorp Ab | Kylsystemsarbetsfluid innehållande som smörjmedel en hyperförgrenad makromolekyl av polyestertyp |
DE102006040122B3 (de) * | 2006-08-26 | 2007-10-31 | Degussa Gmbh | Enteisungsmittel und/oder Vereisungsschutzmittel |
CN100529112C (zh) | 2007-06-01 | 2009-08-19 | 株洲成华实业有限公司 | 一种水溶性淬火介质 |
US9284625B2 (en) * | 2007-11-20 | 2016-03-15 | Nalco Company | Use of polyols as scale control reagents in the mining processes |
JP5502349B2 (ja) * | 2009-03-13 | 2014-05-28 | 出光興産株式会社 | 水系潤滑剤 |
US8101045B2 (en) * | 2010-01-05 | 2012-01-24 | Nalco Company | Modifying agent for yankee coatings |
-
2010
- 2010-02-22 JP JP2010035690A patent/JP5475497B2/ja not_active Expired - Fee Related
-
2011
- 2011-02-22 WO PCT/JP2011/053778 patent/WO2011102523A1/ja active Application Filing
- 2011-02-22 CN CN201180010380.1A patent/CN102753709B/zh not_active Expired - Fee Related
- 2011-02-22 US US13/580,305 patent/US9023234B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50109106A (ja) * | 1974-02-01 | 1975-08-28 | ||
JPS60501316A (ja) * | 1983-05-18 | 1985-08-15 | イ−・エフ・ホ−トン・アンド・カンパニ− | 置換オキサゾリン重合体を使用した急冷方法 |
JPH01100217A (ja) * | 1987-10-14 | 1989-04-18 | Idemitsu Kosan Co Ltd | 焼入剤 |
JPH09227932A (ja) * | 1996-02-21 | 1997-09-02 | Idemitsu Kosan Co Ltd | 水溶性焼入れ液 |
JP2002265973A (ja) * | 2001-03-07 | 2002-09-18 | Daido Chem Ind Co Ltd | 水溶性熱処理液 |
JP2009185179A (ja) * | 2008-02-06 | 2009-08-20 | Nagasaki Univ | 多分岐性高分子及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2011168860A (ja) | 2011-09-01 |
CN102753709A (zh) | 2012-10-24 |
US9023234B2 (en) | 2015-05-05 |
CN102753709B (zh) | 2014-08-20 |
JP5475497B2 (ja) | 2014-04-16 |
US20130001461A1 (en) | 2013-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5475497B2 (ja) | 水系熱処理液組成物 | |
CN105366823B (zh) | 无磷缓蚀阻垢剂组合物和无磷缓蚀阻垢剂及其应用和共聚物在缓蚀中的应用 | |
US10472585B2 (en) | Aqueous lubricant for plastic working of metal material and having superior gas clogging resistance and post-moisture absorption workability | |
CN104193963B (zh) | 一种阳离子型水性环氧乳液 | |
WO2008089130A1 (en) | Lubricant compositions and methods of making same | |
CN110747319B (zh) | 一种超速淬火油及其制备方法 | |
EP2132251B1 (en) | Composition and method | |
CN104726656A (zh) | 一种用于铝合金精密零件的水溶性淬火介质 | |
Yu et al. | “Nascent” Cu (0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature | |
EP3763779A1 (en) | Lubricant composition and method of preparing copolymer using the same | |
EP3907269B1 (en) | Hydrogenated linear polydiene copolymers as base stock or lubricant additives for lubricant compositions | |
EP2914639B1 (en) | Process for preparing low sulfur dispersant polymers | |
JP2011132284A (ja) | 抗乳化剤、その製造法及びそれを含有する水溶性加工油剤組成物 | |
WO2017063188A1 (en) | Maleic anhydride homopolymer and maleic acid homopolymer and the method for preparing the same, and non-phosphorus corrosion inhibitor and the use thereof | |
JP2012153809A (ja) | 水溶性焼入液組成物 | |
Kang et al. | Solution behavior of two novel anionic polyacrylamide copolymers hydrophobically modified with n‐benzyl‐n‐octylacrylamide | |
CN102408323A (zh) | 一种用于丙烯酸精制过程的超强多功能阻聚剂的制备及其使用方法 | |
JP6190287B2 (ja) | 水系潤滑剤 | |
WO2018101342A1 (ja) | メタクリル系共重合体溶液の製造方法 | |
CN1860199A (zh) | 冷却剂组合物 | |
JP6787594B2 (ja) | 水溶性焼入れ油組成物 | |
JP2015166481A (ja) | 水系熱処理液用冷却剤、水系熱処理液および熱処理方法 | |
JP6355033B1 (ja) | 水溶性熱処理剤組成物 | |
CN112679723B (zh) | 一种两端烷基封端pag聚醚及其制备方法 | |
EP3914678B1 (en) | Lubricant base stock |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180010380.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11744809 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13580305 Country of ref document: US Ref document number: 2311/KOLNP/2012 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11744809 Country of ref document: EP Kind code of ref document: A1 |